WO2021113489A1 - Vernis d'acide polyamique préparé à partir de dianhydride de bisphénol a de haute pureté et articles préparés à partir de celui-ci - Google Patents

Vernis d'acide polyamique préparé à partir de dianhydride de bisphénol a de haute pureté et articles préparés à partir de celui-ci Download PDF

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WO2021113489A1
WO2021113489A1 PCT/US2020/063078 US2020063078W WO2021113489A1 WO 2021113489 A1 WO2021113489 A1 WO 2021113489A1 US 2020063078 W US2020063078 W US 2020063078W WO 2021113489 A1 WO2021113489 A1 WO 2021113489A1
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bis
ions
ppm
methylethylidene
isobenzofurandione
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PCT/US2020/063078
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English (en)
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Lucas Robert BUFALINI
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Shpp Global Technologies B.V.
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Publication of WO2021113489A1 publication Critical patent/WO2021113489A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • EP19213248.8 filed on December 3, 2019, the entire content of which is incorporated by reference herein.
  • Polyimides and in particular, polyetherimide (PEI), are high performance polymers having a high glass transition temperature (T g ) depending on the monomers used to prepare the polymers. These polymers further have high strength, heat resistance, and modulus, and broad chemical resistance. PEIs are widely used in applications as diverse as automotive and electrical/electronic applications since these compositions offer good mechanical, electrical, and thermal properties.
  • PEIs as well as copolymers thereof, have shown versatility in various manufacturing processes, proving amenable to techniques including injection molding, extrusion, and thermoforming, to prepare various articles including layers, fibers, and composite materials.
  • PEIs can be prepared by condensation polymerization, for example of a dianhydride with a diamine.
  • condensation polymerization for example of a dianhydride with a diamine.
  • high purity monomer components are desirable. Additionally, some applications can require that the polymers have good optical clarity, and good thermal and mechanical properties.
  • a varnish composition comprising a polyamic acid comprising structural units derived from reaction of 5,5'-[l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3- isobenzofurandione composition with an organic diamine; and a solvent, wherein the 5,5'-[l- methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione composition comprises: 25 ppm or less, or 0.01 to 25 ppm each of sodium ions, potassium ions, calcium ions, zinc ions, aluminum ions, titanium ions, iron ions, chromium ions, molybdenum ions, nickel ions, and phosphorus ions;
  • each of phosphate ions, sulfate ions, chloride ions, nitrate ions, and nitrite ions 0.0001 to 10 wt%, or 0.1 to 10 wt%, or 0.25 to 2 wt%, or 0.25 to 1 wt% of residual 4,4'- BPA tetraacid; 0.0001 to 10 wt%, or 0.1 to 10 wt%, or 0.25 to 2 wt%, or 0.25 to 1 wt% of residual 4,4'-BPA diacid; and 0.00001 to 4 wt%, or 0.01 to 4 wt%, or 0.01 to 2 wt%, or 0.05 to 1 wt% of residual 4,4'-BPA imide-anhydride, wherein each amount is based on the total weight of the 5,5'-[l- methylethylidene)bis(4,l-phenyleneoxy)bis-l,3
  • an article manufactured from the varnish composition preferably wherein the article is a fiber, a layer, a coating, a cast article, a prepreg, a composite, or a laminate.
  • a cured product of the varnish composition comprising a peel strength of greater than 1.3 N/mm, or greater than 1.35 N/mm, or greater than 1.4 N/mm, as determined according to IPC 2.4.8; or a thickness of 0.1 to 1,000 micrometers, or 0.1 to 500 micrometers, or 0.1 to 250 micrometers; or a dielectric constant of 2 to 5, or 2.5 to 4, or 2.8 to 3.2 when measured at 10 GHz and 23 °C, as determined by dielectric spectroscopy; or a dissipation factor of 0.00001 to 0.01, or 0.001 to 0.01, or 0.001 to 0.008 when measure at 10 GHz and 23 °C, as determined by dielectric spectroscopy; a glass transition temperature of 150 to 300°C, or 190 to 300°C, or 200 to 300°C, or 210 to 300°C, as determined by digital scanning calorimetry (DSC); or a combination thereof.
  • DSC digital scanning calorimetry
  • Also provided is a method of manufacturing an article from the varnish composition comprising disposing the varnish composition on a substrate; and curing the varnish composition to form the article; preferably wherein the article is a fiber, a layer, a coating, a cast article, a prepreg, a composite, or a laminate.
  • a varnish composition including a polyamic acid and a solvent.
  • the polyamic acid includes structural units derived from reaction of a high purity 5,5'-[l- methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione (also referred to as 4,4'-(4,4'- isopropylidenediphenoxy)bis(phthalic anhydride), 4,4'-bisphenol A dianhydride, or 4,4'-BPADA) with an organic diamine.
  • the purified 4,4'-BPADA also referred to herein as the 4,4’-isomer, is substantially free from contaminants such as phase transfer agents, various inorganic ionic species including sodium, potassium, calcium, zinc, aluminum, titanium, iron, chromium, molybdenum, nickel, phosphorus, phosphate, nitrate, nitrite, sulfate, and chloride ions, imide-anhydrides, and diacid derivatives resulting from ring opening of an anhydride moiety.
  • phase transfer agents various inorganic ionic species including sodium, potassium, calcium, zinc, aluminum, titanium, iron, chromium, molybdenum, nickel, phosphorus, phosphate, nitrate, nitrite, sulfate, and chloride ions, imide-anhydrides, and diacid derivatives resulting from ring opening of an anhydride moiety.
  • various inorganic ionic species including sodium, potassium, calcium, zinc, aluminum, titanium, iron, chro
  • the varnish composition includes a polyamic acid comprising structural units derived from reaction of a 4,4'-BPADA composition with an organic diamine; and a solvent.
  • the polyamic acid is derived from a purified 4,4'-BPADA composition that is substantially free of impurities.
  • the 4,4'-BPADA is of formula (1)
  • the purified 4,4'-BPADA composition includes the 4,4'-BPADA; 25 parts per million by weight (ppm) or less, or 0.01 to 25 ppm, or 0.01 to 10 ppm each of sodium ions, potassium ions, calcium ions, zinc ions, aluminum ions, titanium ions, iron ions, chromium ions, molybdenum ions, nickel ions, and phosphorus ions; 50 ppm or less, or 0.01 to 50 ppm, or 0.01 to 25 ppm each of phosphate ions, sulfate ions, chloride ions, nitrate ions, and nitrite ions; 0.0001 to 10 wt%, or 0.1 to 10 wt%, or 0.25 to 2 wt%, or 0.25 to 1 wt%, or 0.0001 to 0.3 wt% of residual 4,4'- BPA tetraacid (4,4'-BPA-TA); 0.0001 to 10 wt%, or
  • the purified 4,4'-BPADA is a composition that comprises the 4,4'-BPADA and the recited impurities as described herein.
  • the amounts in weight percent and ppm are based on the total weight of the purified 4,4'-BPADA composition.
  • purified 4,4'-BPADA is used for convenience. However, given the presence of one or more impurities in the purified 4,4'-BPADA, for the sake of convenience the term “purified 4,4'-BPADA” is used interchangeably with the term “purified 4,4'- BPADA composition.”
  • the purified 4,4'-BPADA includes 0.01 to 25 ppm, or 0.01 to 15 ppm, or 0.01 to 10 ppm total of sodium ions, potassium ions, calcium ions, zinc ions, aluminum ions, titanium ions, iron ions, chromium ions, molybdenum ions, nickel ions, and phosphorus ions combined, based on the total weight of the purified 4,4'-BPADA.
  • the purified 4,4'-BPADA includes 0.01 to 25 ppm, or 0.01 to 15 ppm, or 0.01 to 10 ppm total of phosphate ions, sulfate ions, chloride ions, nitrate ions, and nitrite ions combined, based on the total weight of the purified 4,4'-BPADA.
  • the purified 4,4'-BPADA includes 0.0002 to 10 wt%, or 0.1 to 10 wt%, or 0.25 to 2 wt%, or 0.25 to 1 wt%, or 0.0002 to 0.3 wt% of 4,4'-BPA-TA and 4,4'-BPA-DA combined; 0.01 to 50 ppm, or 0.01 to 25 ppm of sulfate ions; 0.01 to 25 ppm, or 0.01 to 10 ppm of sodium ions; and 0.01 to 25 ppm, or 0.01 to 10 ppm of chloride ions.
  • the amounts in weight percent and ppm are based on the total weight of the purified 4,4'-BPADA.
  • the purified 4,4'-BPADA includes 15 ppm or less, or 0.01 to 15 ppm, or 0.01 to 10 ppm of sulfate ions; 10 ppm or less, or 0.01 to 10 ppm, or 0.01 to 5 ppm of sodium ions; 5 ppm or less, or 0.01 to 5 ppm, or 0.01 to 2 ppm of chloride ions; 2 ppm or less, or 0.01 to 2 ppm, or 0.01 to 1 ppm of nitrate ions; and 2 ppm or less, or 0.01 to 2 ppm, or 0.1 to 1 ppm of nitrite ions.
  • the amounts in weight percent and ppm are based on the total weight of the purified 4,4'-BPADA.
  • the residual levels of cations can be determined by inductively coupled plasma-digestion (ICP-Dig).
  • ICP-Dig inductively coupled plasma-digestion
  • the residual levels of anions can be determined by extraction-ion chromatography (IC-Extract).
  • the residual 4,4'-BPA tetraacid (4,4'-BPA-TA) is a compound of formula (2):
  • the residual 4,4'-BPA anhydride diacid (4,4'-BPA-DA) is a compound of formula (3):
  • the residual 4,4'-BPA imi de-anhydride (4,4'-BPA-IA) is a compound of formula (4): wherein R is hydrogen, or a Ci-30 substituted or unsubstituted hydrocarbyl, preferably a Ci_6 alkyl or a C6-20 aryl optionally substituted with 1 to 5 halogens, Ci_ 6 alkyl groups, or a combination thereof.
  • R is methyl.
  • the purified 4,4'-BPADA can further include 0.0001 to 6 wt%, or 0.01 to 6 wt%, or 0.01 to 2 wt%, or 0.01 to 1 wt%, or 0.01 to 0.5 wt%, or 0.01 to 0.1 wt% of a combination of 3,4'-BPADA (0.01 to 6 wt%) of formula (5a), 3,3'-BPADA of formula (5b), 3,4'- BPA-IA of formula (6a) or (6b), or a combination thereof.
  • the amounts in weight percent are based on the total weight of the purified 4,4'-BPADA. wherein R is the same as defined for formula (4).
  • the purified 4,4'-BPADA obtained by a high purity hydrolysis ring closure process is >99 wt% of the 4,4'-isomer, preferably >99.5 wt% of the 4,4'-isomer.
  • the residual amounts of 4,4'-BPA-TA, 4,4'-BPA-DA, 4,4'-BPA-IA, 3,4'-BPADA, and 3,4'-BPA-IA can be determined by ultra-performance liquid chromatography (UPLC) or carbon- 13 nuclear magnetic resonance ( 13 C NMR).
  • UPLC ultra-performance liquid chromatography
  • 13 C NMR carbon- 13 nuclear magnetic resonance
  • the varnish composition can have a dynamic viscosity of 20,000 to 120,000 cP, or 20,000 to 80,000 centipoise (cP), as determined at a solids content of 10 wt% in 1-methylpyrrolidin- 2-one (NMP) at 25°C.
  • the varnish composition can have a dynamic viscosity of 20,000 to 120,000 cP, or 30,000 to 120,000 cP, or 20,000 to 80,000 cP, 30,000 to 80,000 cP, or 40,000 to 80,000 cP, or 50,000 to 80,000 cP, or 50,000 to 70,000 cP as determined at a solids content of 10 wt% in NMP at 25°C.
  • the varnish composition prepared from the purified 4,4'-BPADA provides a higher dynamic viscosity than expected for such polyamic acid solutions, which are generally less than 20,000 cP when determined at a solids content of 10 wt% in NMP at 25°C. This discovery allows the provision of a high viscosity polyamic acid solution that can be used advantageously for various applications.
  • the varnish composition includes a polyamic acid prepared from a purified 4,4'-BPADA comprising 0.00002 to 4 wt%, or 0.1 to 10 wt%, or 0.25 to 2 wt%, or 0.25 to 1 wt%, or 0.0002 to 0.3 wt% of 4,4'-BPA-TA and 4,4'-BPA-DA combined; 0.01 to 50 ppm, or 0.01 to 25 ppm of sulfate ions; 0.01 to 25 ppm, or 0.01 to 10 ppm of sodium ions; and 0.01 to 25 ppm, or 0.01 to 10 ppm of chloride ions; wherein the varnish composition has a dynamic viscosity of 30,000 to 120,000 cP, or 30,000 cP to 80,000 cP, or 50,000 to 80,000 cP, or 50,000 to 70,000 cP, as determined at a solids content of 10 wt% in NMP at 25°C.
  • the varnish composition can include a polyamic acid comprising structural units derived from reaction of 5,5'-[l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3- isobenzofurandione composition with an organic diamine; and a solvent, wherein the 5,5'-[l- methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione composition comprises: greater than or equal to 99 wt%, preferably greater than or equal to 99.5 wt% of the 5,5'-[l- methylethylidene)bis(4,l-phenyleneoxy)bis- 1,3 -isobenzofurandione; 0.01 to 25 ppm each of sodium ions, potassium ions, calcium ions, zinc ions, aluminum ions, titanium ions, iron ions, chromium ions, molybdenum ions, nickel ions, and phosphorus ions; 0.
  • each amount is based on the total weight of the 5,5'-[l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione composition, wherein the 5,5'-[l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione composition is made by a method comprising: hydrolyzing a 4,4'-BPADA-bisimide to form
  • the purified 4,4'-BPADA can be particularly useful for the preparation of a polyetherimide. Accordingly, provided is a polyetherimide comprising repeating units derived from polymerization of the purified 4,4'-BPADA and an organic diamine. It is to be understood that the term “polymerization of the purified 4,4'-BPADA and an organic diamine” refers to the formation of a polyamic acid and imidization of the polyamic acid as described herein.
  • the 4,4'-BPADA can be prepared according to the methods described herein and can therefore advantageously possess low levels of contaminants.
  • the organic diamine used to prepare the polyamic acid of the varnish compound includes one or more diamines that are each independently of formula (7)
  • R is a C 6-30 aromatic or heteroaromatic hydrocarbon, a straight or branched chain C 4.20 alkylene, a C3.8 cycloalkylene, or a halogenated derivative thereof.
  • R is meta-phenylene, para-phenylene, or a diarylene sulfone, in particular bis(4,4’-phenylene)sulfone, bis(3,4’-phenylene)sulfone, bis(3,3’-phenylene)sulfone, or a combination thereof.
  • at least 10 mole percent (mol%) or at least 50 mol% of the R groups contain sulfone groups, and in other aspects no R groups contain sulfone groups.
  • Exemplary organic diamines include, but are not limited to, 1,4-butane diamine, 1,5- pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3- methylheptamethylenedi amine, 4,4-dimethylheptamethylenediamine, 4- methylnonamethylenediamine, 5-methylnonamethylenediamine, 2,5- dimethylhexamethylenedi amine, 2,5-dimethylheptamethylenediamine, 2, 2- dimethylpropylenediamine, N-methyl-bis (3-aminopropyl) amine, 3-methoxyhexamethylenediamine, l,2-bis(3-aminopropoxy) ethane, l,3-bis(4-aminophenoxy)benzene,
  • the organic diamine is meta-phenylene diamine, para-phenylene diamine, ortho-phenylene diamine, 4,4'-diamino- diphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4, 4'-oxy dianiline, 1,3- bis(4-aminophenoxy)benzene, or a combination thereof.
  • the organic diamine is m- phenylene-diamine, p-phenylenediamine, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3 '-diamino-diphenyl sulfone, or a combination thereof.
  • the purified 4,4'-BPADA can be prepared by a hydrolysis ring closure route that includes the steps of hydrolysis of a 2-hydrocarbyl-5-[4-[2-[4-(2-hydrocarbyl-l,3-dioxoisoindol-5- yl)oxyphenyl]-propan-2-yl]phenoxy]isoindole-l,3-dione (also known as 2,2-bis[4-(V- hydrocarbylphthalimido-4-oxy)phenyl]propane or 4,4'-BPA-bisimide) to the corresponding tetraacid salt followed by acidification and dehydration to form BPADA (as described, for example, in U.S.
  • the 4,4'-BPADA- bisimide is of formula (8) wherein R is hydrogen, or a Ci- 30 substituted or unsubstituted hydrocarbyl, preferably a C M alkyl or a C 6-20 aryl optionally substituted with 1 to 5 halogens, C M alkyl groups, or a combination thereof.
  • R is methyl.
  • purified 4,4'-BPADA can be prepared by a method including hydrolyzing a 4,4'-BPADA-bisimide to form the corresponding 4,4'-BPADA-TA tetrasalt, quenching the 4,4'-BPADA-TA tetrasalt with a mineral acid to form the 4,4'-BPADA-TA, contacting the 4,4'- BPADA-TA with a halogenated solvent to form a reaction mixture; heating the reaction mixture to a temperature effective to form the corresponding 4,4'-BPADA from the 4,4'-BPADA-TA, optionally in the presence of an aliphatic carboxylic acid, a corresponding aliphatic anhydride, or a mineral acid; and isolating the purified 4,4'-BPADA from the reaction mixture.
  • the method of making the purified 4,4'-BPADA composition is preferably conducted in the absence of an organic acid, an organic acid anhydride, or both.
  • An exemplary 4,4'-BPADA-TA tetrasalt is the tetrasodium salt of formula (9):
  • the hydrolyzing of the 4,4'-BPADA-bisimide can be performed in the presence of 4 to 100, 4 to 50, 4 to 25, 4 to 10, 4 to 6, or 4 to 5 equivalents of a base, based on the 4,4'-BPADA- bisimide, for example an alkali metal hydroxide (such as sodium hydroxide or potassium hydroxide).
  • the hydrolyzing can be performed under aqueous conditions for an effective amount of time, for example 1 to 10 hours, or 2 to 8 hours, at atmospheric pressure or elevated pressure.
  • Organic co solvents can optionally be added.
  • Exemplary organic solvents include optionally substituted Ci- 6 aliphatic alcohol such as methanol, ethanol, isopropanol, ethylene glycol, higher poly(alkylene glycol)s, or 1 -butanol.
  • Organic co-solvents can optionally be added.
  • the hydrolyzing can be conducted at a temperature of 65 to 200°C, or 75 to 130°C, and optionally at elevated pressure.
  • the mineral acid can be HC1, H 2 SO 4 , H 3 PO 4 , HNO 3 , or the like.
  • the acid can be present in an amount of 2 to 10 molar equivalents, 3 to 8 molar equivalents, or 4 to 8 molar equivalents based on the 4,4'-BPADA-bisimide.
  • the halogenated solvent can be an aromatic halogenated solvent, for example, ortho dichlorobenzene, para-dichlorobenzene, meta-dichlorobenzene, trichlorobenzene, or a combination thereof.
  • the 4,4'-BPADA can be further purified.
  • the method for purification can include contacting the dianhydride with a halogenated solvent to form a solution.
  • the method can further include one or more of filtering the solution to remove ionic species; washing the solution with aqueous media to remove ionic species; crystallizing the dianhydride from the solution to remove ionic species; and contacting the solution with an adsorbent to remove ionic species.
  • the filtering can include passing the solution through a filter having a pore size of less than or equal to 2 micrometers (pm), or less than 1 pm, or 0.2 to 0.45 pm.
  • the crystallizing can include adding an antisolvent to the solution and cooling the solution to a temperature effective to provide a slurry, such as to temperature of 20 to 100°C, or 50 to 100°C, or 65 to 85°C.
  • the antisolvent can be a non-polar solvent, such as heptane, hexane, pentane, benzene, ligroin, or a combination thereof.
  • the adsorbent can be, for example, diatomaceous earth, silica, alumina, ion-exchange resin, or a combination thereof, and the solution comprising the adsorbent can be filtered through a filter having a pore size of 60 pm or less, or 40 to 60 pm.
  • the solvent of the varnish composition can be, for example, N,N- dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N- dimethylmethoxyacetamide, N-methyl-2-pyrrolid-one, N-cyclohexylpyrrolidinone, N- methylcaprolactam, l,3-dimethyl-2-imidazolidone, 1 ,2-dimethoxy-ethane, 1,3-dioxane, 1,4-dioxane, tetrahydrofuran, g-butyrolactone, g-caprolactone, dimethyl-sulfoxide, benzophenone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diglyme, triglyme, tetra-glyme, N,N- dimethylethyleneurea, N,N-dimethylpropyleneurea,
  • the solvent is anhydrous and does not include water.
  • the solvent can include less than 100 ppm, or less than 50 ppm, or less than 10 ppm of water.
  • the amount of solvent in the varnish composition which is generally the same amount of solvent used to prepare the polyamic acid, is not particularly limited.
  • the solids content can be from 1 to 35 wt%, based on the total weight of the varnish composition.
  • the solids content can be from 1 to 30 wt%, 10 to 30 wt%, 20 to 30 wt%, 10 to 25 wt%, 10 to 20 wt%, or 5 to 15 wt%, based on the total weight of the varnish composition.
  • the polyamic acid of the varnish composition can be prepared by combining the purified 4,4'-BPADA, the organic diamine and optionally other diamine components, and the solvent by stirring until a viscous solution is formed.
  • a method of manufacturing the varnish composition can include combining the components of the varnish composition, and heating the components with agitation or stirring at a temperature and for a period of time effective to dissolve the components in the solvent, or at a temperature lower than the boiling point of the solvent.
  • the temperature is not particularly limited, and can be selected to avoid instability of the polyamic acid.
  • the temperature is 50°C or less, or 30°C or less, or 25°C or less.
  • the organic diamine component can be included in an amount of from 0.5 to 2.0 moles, or from 0.8 to 1.5, or from 0.9 to 1.1 moles, or 0.999 to 1.001 moles per mole of dianhydride component.
  • the poly condensation to form the polyamic acid of the varnish composition is exothermic and the reaction mixture can be cooled to below room temperature as appropriate.
  • the varnish composition can be prepared from a combination of 40 wt% or greater of the combined dianhydride and organic diamine, based on the total weight of the dianhydride, organic diamine, and solvent.
  • an end-capping agent is present during the reaction to control the molecular weight of the polyamic acids and thus the polyetherimides formed from the polyamic acids.
  • Exemplary end capping agents include, but are not limited to phthalic anhydride, substituted mono anhydrides, aniline, Ci-Cig linear, branched or cyclic aliphatic monoamines, and monofunctional aromatic amines.
  • the end capping agent is phthalic anhydride and the varnish composition includes 0.01 to 4 mol%, or 0.01 to 2 mol%, or 0.05 to 1 mol% of residual phthalic anhydride, based on the total weight of the purified 4,4'-BPADA.
  • the purified 4,4'-BPADA composition may include greater than or equal to 99.5 wt% of the 4,4'-BPADA and the end capping agent may be phthalic anhydride, wherein the varnish composition may include 0.01 to 0.5 mol%, or 0.01 to 0.5 mol%, or 0.05 to 0.5 mol% of residual phthalic anhydride, based on the total weight of the purified 4,4'-BPADA composition.
  • the cured varnish composition forms a polyetherimide.
  • the cured varnish composition can advantageously have low levels of residual impurities.
  • the cured product includes less than 25 ppm, for example 0.01 to 25 ppm each of sodium ions, potassium ions, calcium ions, zinc ions, aluminum ions, titanium ions, iron ions, chromium, molybdenum, nickel, and phosphorus ions, and less than 50 ppm, for example 0.01 to 50 ppm each of phosphate ions, sulfate ions, chloride ions, nitrate ions, and nitrite ions.
  • the polyetherimides can have a melt index of 0.1 to 10 grams per minute (g/min), as measured by ASTM D1238 at 340 to 370°C, using a 6.7-kilogram (kg) weight.
  • the polyetherimide has a weight average molecular weight (M w ) of 1,000 to 500,000 grams/mole (g/mol), as measured by gel permeation chromatography (GPC), using polystyrene standards.
  • MPC gel permeation chromatography
  • the polyetherimide has an Mw of 10,000 to 250,000 g/mol, or 25,000 to 200,000 g/mol, or 50,000 to 200,000 g/mol.
  • Such polyetherimides can have an intrinsic viscosity greater than 0.2 deciliters per gram (dL/g), or, more specifically, 0.35 to 0.7 dL/g as measured in m-cresol at 25°C.
  • the varnish composition can be used in the manufacture of articles useful for a wide variety of applications.
  • An article can be manufactured from the varnish composition by, for example, forming the article from the varnish composition, for example by casting, molding, extruding, or the like, and removing the solvent from the formed article.
  • Exemplary articles can be in the form of a fiber, a layer, a conformal coating, a cast article, a prepreg, or a cured composite.
  • the article can be a layer, and can be formed by casting the varnish composition onto a substrate to form a cast layer.
  • the solvent can be removed by any number of means, including by heating the cast layer, heating the cast layer under heat and pressure, for example by laminating the cast layer to another substrate.
  • articles prepared by the above-described methods can include adhesives, packaging material, capacitor films, or circuit board layers.
  • articles prepared from the varnish composition can be a polyetherimide dielectric layer, or a coating disposed on a substrate, for example a wire or cable coating.
  • the article can be a polyetherimide dielectric layer in a circuit material, for example in a printed circuit board, used, for example, in lighting or communications applications.
  • Other exemplary articles prepared from the varnish composition can be painted layers to inhibit corrosion, coatings to provide thermal resistance, coatings for smoothing a surface, or the like.
  • the article can further comprise a fibrous preform, for example, a fibrous preform comprising any one or more of the above-described fabrics.
  • the method of manufacturing the article can include forming the article from the varnish composition by coating or impregnating the preform with the varnish.
  • the impregnated fibrous preform can optionally be shaped before or after removing the solvent.
  • articles prepared from a varnish composition that further comprises a thermosetting polymer composition can further comprise partially curing the thermosetting polymer composition to form a prepreg, or fully curing the thermosetting polymer composition to form a composite article.
  • the curing can be before or after removing the solvent from the varnish composition.
  • the article can be further shaped before removal of the solvent or after removal of the solvent, before curing, after partial curing, or after full curing, for example by thermoforming.
  • the article is formed, and the solvent is removed; the article is partially cured (B-staged); optionally shaped; and then further cured.
  • thermosetting polymers include epoxy resin, polyester resin, polyimide resin, bis-maleimide resin, cyanate ester resin, vinyl resin, benzoxazine resin, benzocyclobutene resin, phenol resin, urea resin, melamine-formaldehyde resin, urea-formaldehyde latex, xylene resin, diallylphthalate resin, aniline resin, furan resin, polyurethane, mineral filled silicone, or a combination thereof.
  • the polyetherimide dielectric layer further comprises a thermoset polymer
  • the thermoset polymer can be uncured or partially cured before laminating, and fully cured during or after the laminating. Alternatively, the thermosetting polymer can be fully cured prior to lamination.
  • thermosetting polymer can be partially cured during and/or after solvent removal, or the thermosetting polymer can be fully cured during or after solvent removal. Following removal of the solvent and fully curing the thermosetting polymer, the resulting polyetherimide layer can have at least one of improved flame retardance, improved toughness, and improved peel strength from copper, compared to the thermosetting polymer alone.
  • Exemplary articles prepared from the varnish composition for various applications can include copper clad laminates (CCL), for example, metal core copper clad laminates (MCCCL), composite articles, and coated articles, for example multilayer articles. Methods of manufacturing such articles represent another aspect of the disclosure.
  • CCL copper clad laminates
  • MCCL metal core copper clad laminates
  • coated articles for example multilayer articles.
  • a polyetherimide dielectric layer prepared from the above- described varnish composition can be useful in a circuit assembly, for example, in a metal-clad laminate such as a copper clad laminate.
  • a laminate can comprise a polyetherimide dielectric layer, a conductive metal circuit layer disposed on the polyetherimide dielectric layer, and optionally, a heat dissipating metal matrix layer disposed on the dielectric layer on a side opposite the conductive metal layer.
  • the polyetherimide dielectric layer can optionally comprise a fibrous preform (e.g., a fabric layer) and/or a thermosetting polymer composition.
  • the polyetherimide dielectric layer can further comprise a glass fabric layer or a cured thermoset polymer.
  • the conductive metal layer can be in the form of a circuit, and can be copper, zinc, tin, brass, chromium, molybdenum, nickel, cobalt, aluminum, stainless steel, iron, gold, silver, platinum, titanium, or an alloy containing one or more of these metals.
  • exemplary metal layers comprise copper or a copper alloy.
  • wrought copper foils can be used.
  • the conductive metal layer comprises copper and the laminate is a copper clad laminate.
  • Conductive metal layers can have a thickness of 2 to 200 micrometers (pm), specifically 5 to 50 pm, and more specifically 5 to 40 pm.
  • a heat dissipating metal matrix layer can be a thermally conductive metal such as aluminum, boron nitride, aluminum nitride, copper, iron, steel, or the like.
  • a thermally conductive, electrically conductive metal can be used provided that the metal is electrically isolated from the metal circuit layer.
  • Preferred supporting metal matrix layers can have a thickness of 0.1 to 20 millimeters (mm), specifically 0.5 to 10 mm, and more specifically 0.8 to 2 mm.
  • the metal matrix layer comprises aluminum.
  • the conductive metal layer and the supporting metal matrix layers can be pretreated to have high surface roughness for enhanced adhesion to the dielectric layer.
  • Treatment methods include washing, flame treatment, plasma discharge, corona discharge, or the like, for example to enhance adhesion of the metal layer.
  • the dielectric layer can adhere firmly to the conductive metal layer or the heat dissipation layer without using an adhesive.
  • an adhesive can be used to improve adhesion of the dielectric layer to the conductive metal layer or the heat dissipation layer.
  • Exemplary adhesives used to bond the composite sheet to a metal are polyimide adhesives, acrylic adhesives, or epoxies.
  • the copper clad laminates can be made by thermal lamination of one or more dielectric layers, one or more conductive metal layers, and a supporting metal matrix layer, under pressure without using thermosetting adhesives.
  • the dielectric layer can be prepared from the varnish composition, and this layer can be prepared prior to the thermal lamination step, for example, by a solvent casting process to form the dielectric layer.
  • the dielectric layer, the conductive metal layer, and the thermal dissipation layer are thermally laminated together by an adhesive-free process under pressure to form a laminate.
  • a dielectric layer is placed between the conductive metal layer and a layer of woven fabric, and thermally laminated under pressure in a single step.
  • the conductive metal layer can optionally be in the form of a circuit before laminating.
  • the conductive metal layer can optionally be etched to form the electrical circuit following lamination.
  • the laminating can be by hot press or roll calendaring methods, for example, a roll-to-roll method.
  • laminates for a circuit assembly can be made by a solution casting method in which the varnish composition is cast directly onto the conductive metal layer, followed by lamination to the heat dissipating metal matrix layer.
  • the varnish composition can be cast directly onto the heat dissipating metal matrix layer, followed by lamination to the electrically conductive metal layer.
  • Multilayer laminates comprising additional layers can also be made by thermal lamination in one step or in two or more consecutive steps by such processes as hot press or roll calendaring methods. In some aspects, seven layers or fewer can be present in the laminate and in other aspects, sixteen layers or fewer.
  • a laminate can be formed in one step or in two or more consecutive steps with sequential layers of fabric-dielectric layer-conductive metal layer- dielectric layer-fabric-dielectric layer-metal foil, or a sub-combination thereof with fewer layers, such that the laminate comprises a dielectric layer comprising a film derived from the varnish composition between any conductive metal layer and any fabric layer.
  • a first laminate can be formed in one step or in two or more consecutive steps with a layer of fabric between two dielectric layers, such as a layer of a woven glass fabric disposed between two dielectric layers.
  • a second laminate can then be prepared by laminating a conductive metal layer to a dielectric layer of the first laminate.
  • the laminates can be prepared by a method comprising the steps of laminating the polyetherimide dielectric layer to the conductive metal circuit layer under heat, pressure, or a combination thereof, and optionally, subsequently, or simultaneously laminating the polyetherimide dielectric layer to the heat dissipating supporting metal matrix layer.
  • the supporting metal matrix layer is disposed on the polyetherimide layer in a side opposite the conductive metal layer.
  • the polyetherimide layer can be prepared by casting the varnish composition onto a substrate, and removing solvent from the cast layer. Alternatively, the varnish composition can be directly cast onto a conductive metal circuit layer, and the solvent can be removed to provide the polyetherimide dielectric layer.
  • the polyetherimide layer can further comprise a woven or nonwoven glass fabric.
  • the polyetherimide layer can be prepared by impregnating the glass fabric with a varnish composition, and removing the solvent from the impregnated glass fabric.
  • the conductive metal layer in a copper clad laminate can further be patterned to provide a printed circuit board. Furthermore, the copper clad laminates can be shaped to provide a circuit board having the shape of a sheet, a tube, or a rod. The copper clad laminates can have a thermal conductivity of greater than or equal to 0.3 W/m-K.
  • Printed circuit boards prepared from the varnish composition can have an overall thickness of 0.1 to 20 millimeters (mm), and specifically 0.5 to 10 mm, wherein overall thickness refers to an assembly comprising a layer each of the polyetherimide dielectric layer, the electrically conductive metal layer, and the supporting metal matrix layer. Circuit assemblies can have an overall thickness of 0.5 to 2 mm, and specifically 0.5 to 1.5.
  • the thickness of the polyetherimide dielectric layer can be 5 to 1500 pm, or 5 to 750 pm, or 10 to 150 pm, or 10 to 100 pm.
  • the printed circuit board can be a metal core printed circuit board (MCPCB) for use in a light emitting diode (LED) application.
  • MCPCB metal core printed circuit board
  • Articles include those comprising printed circuits as used in medical or aerospace industries. Still other articles include antennae and like articles. Exemplary articles include, but are not limited to, those comprising printed circuit boards, which are used, for example, in lighting, solar energy, displays, cameras, audio and video equipment, personal computers, mobile telephones, electronic notepads, and like devices, or office automation equipment. For example, electrical parts can be mounted on printed circuit boards comprising a laminate.
  • a method of manufacturing a composite article can comprise impregnating a porous base material with a varnish composition, optionally comprising a thermosetting polymer composition, and subsequently removing the solvent from the impregnated porous base material, and optionally followed by curing.
  • a “porous base material” can be any base material having any size pores or openings that are interconnected or not interconnected.
  • a porous base material may be a fibrous preform or substrate as described above or other porous material comprising a ceramic, a polymer, a glass, carbon, or a combination thereof.
  • the porous base material can be woven or non-woven glass fabric, a fiberglass fabric, or carbon fiber.
  • thermosetting polymer composition can be partially cured to form a prepreg, or can be fully cured to form a reinforced composite article.
  • Removing the solvent from the impregnated porous base material can be achieved by heating, compressing, or heating and compressing the material.
  • the impregnated porous base material can optionally be shaped before or after the partial curing step, and before or after the solvent removal step.
  • the impregnated porous base material can also be shaped after curing, by thermoforming, for example.
  • the composite article prepared by the above-described method can be in the form of a fiber, a layer, a cast article, a prepreg, a wire coating, a molded article, a compression article, or a reinforced composite article.
  • the varnish composition can be used as a coating, for example in the preparation of a multilayer article.
  • a method of manufacturing the coating can comprise the steps of combining the varnish composition and a fluoropolymer (e.g., polytetrafluoroethylene-ethylene copolymers, tetrafluoroethylene-perfluoroalkylvinylether copolymers, tetrafluoroethylene- hexafluoropropylene copolymers, polychlorotrifluoroethylene, tetrafluoroethylene-ethylene copolymers, polyvinylidene fluoride, or a combination thereof), a thermosetting polymer composition (e.g., epoxy resin, polyester resin, polyimide resin, bis-maleimide resin, cyanate ester resin, vinyl resin, benzoxazine resin, benzocyclobutene resin, phenol resin, urea resin, melamine- formaldehyde resin, urea-formaldehyde latex, xylene resin, diallylphthalate resin, aniline resin, furan resin, polyurethane, mineral
  • thermosetting polymer composition a fluoropolymer, or a combination thereof on the primer layer to provide the multilayer article, and optionally thermally treating the multilayer article to cure the thermosetting polymer composition and/or the varnish composition.
  • Removing the solvent from the primer layer can be by heating the layer, compressing the layer, or heating and compressing the layer.
  • the second layer can further comprise the varnish composition.
  • the method of manufacturing the multilayer article can further comprise the step of removing the solvent from the second layer and optionally curing the varnish composition.
  • the varnish composition can be disposed on a substrate and cured to form the polyetherimide dielectric layer.
  • the polyamic acid of the varnish composition can be cured, or imidized, under conditions effective to provide a corresponding polyetherimide.
  • the curing can be performed in the presence of a solvent, and the solvent subsequently removed after curing. Alternatively, at least a portion of the solvent can be removed prior to curing.
  • Conditions effective to cure the varnish composition can include a temperature of 150 to 380°C, and optionally a solids content of 1 to 50 wt%, or 20 to 40 wt%, or 25 to 35 wt%. Curing can be conducted for 1 to 24 hours, or 2 to 24 hours, or 3 to 16 hours.
  • the curing can be conducted at reduced, atmospheric, or elevated pressure.
  • the cured product of the varnish composition can have a peel strength of greater than 1.3 Newtons per millimeter (N/mm), or greater than 1.35 N/mm, or greater than 1.4 N/mm, as determined according to IPC 2.4.8.
  • the cured product of the varnish composition can have a thickness of 0.1 to 1,000 mih, or 0.1 to 500 mih, or 0.1 to 250 mih.
  • the cured product of the varnish composition can have a dielectric constant of 2 to 5, or 2.5 to 4, or 2.8 to 3.2 when measured at 10 gigahertz (GHz) and 23°C, as determined by dielectric spectroscopy.
  • the cured product of the varnish composition can have a dissipation factor of 0.00001 to 0.01, or 0.001 to 0.01, or 0.001 to 0.008 when measure at 10 GHz and 23 °C, as determined by dielectric spectroscopy.
  • the cured product of the varnish composition can have a glass transition temperature of 150 to 300°C, or 190 to 300°C, or 200 to 300°C, or 210 to 300°C, as determined by DSC.
  • the cured product of the varnish composition can have two or more of a peel strength of greater than 1.3 N/mm, or greater than 1.35 N/mm, or greater than 1.4 N/mm, as determined according to IPC 2.4.8; a dielectric constant of 2 to 5, or 2.5 to 4, or 2.8 to 3.2 when measured at 10 GHz and 23°C, as determined by dielectric spectroscopy; a dissipation factor of 0.00001 to 0.01, or 0.001 to 0.01, or 0.001 to 0.008 when measure at 10 GHz and 23 °C, as determined by dielectric spectroscopy; or a glass transition temperature of 150 to 300°C, or 190 to 300°C, or 200 to 300°C, or 210 to 300°C, as determined by DSC; wherein the cured product of the varnish composition can have a thickness of 0.1 to 1,000 pm, or 0.1 to 500 pm, or 0.1 to 250 pm.
  • the cured product of the varnish composition can have three or more of a peel strength of greater than 1.3 N/mm, or greater than 1.35 N/mm, or greater than 1.4 N/mm, as determined according to IPC 2.4.8; a dielectric constant of 2 to 5, or 2.5 to 4, or 2.8 to 3.2 when measured at 10 GHz and 23 °C, as determined by dielectric spectroscopy; a dissipation factor of 0.00001 to 0.01, or 0.001 to 0.01, or 0.001 to 0.008 when measure at 10 GHz and 23 °C, as determined by dielectric spectroscopy; or a glass transition temperature of 190 to 400°C, or 190 to 300°C, or 190 to 260°C, as determined by DSC; wherein the cured product of the varnish composition can have a thickness of 0.1 to 1,000 pm, or 0.1 to 500 pm, or 0.1 to 250 pm.
  • the cured product of the varnish composition has a peel strength of greater than 1.3 N/mm, or greater than 1.35 N/mm, or greater than 1.4 N/mm, as determined according to IPC 2.4.8; a dielectric constant of 2 to 5, or 2.5 to 4, or 2.8 to 3.2 when measured at 10 GHz and 23 °C, as determined by dielectric spectroscopy; a dissipation factor of 0.00001 to 0.01, or 0.001 to 0.01, or 0.001 to 0.008 when measure at 10 GHz and 23 °C, as determined by dielectric spectroscopy; and a glass transition temperature of 150 to 300°C, or 190 to 300°C, or 200 to 300°C, or 210 to 300°C, as determined by DSC; wherein the cured product of the varnish composition can have a thickness of 0.1 to 1,000 pm, or 0.1 to 500 pm, or 0.1 to 250 pm.
  • Example 1 The dynamic viscosities of Example 1 and Comparative Example 1 were obtained using a Brookefield DV3T rheometer operating a CPA-41-Z cone and plate sample cell. Dynamic Viscosities were measured at 25°C in centipoise (cP).
  • UPLC ultra-performance liquid chromatography
  • 13 C NMR carbon-13 nuclear magnetic resonance
  • All residual levels of metals are determined by an inductively coupled plasma-digestion (ICP-Dig) method which uses an ICP spectrometer equipped with: an axial and/or radial viewing, a Gem Cone and/or Ultrasonic nebulizer, and a microwave digestion system equipped with appropriate sample digestion vessels set. Samples are prepared using concentrated nitric acid, hydrochloric acid, sulfuric acid, and/or hydrofluoric acid - Supra pure grades.
  • ICP-Dig inductively coupled plasma-digestion
  • Residual levels of anions are measured by extraction-ion chromatography (IC-Extract).
  • Sample are prepared by dissolving in methylene chloride optionally with HFIP added to help with solubility. The solutions are then extracted with deionized water, and then the aqueous extracts were analyzed using a calibrated Dionex ICS 2000 instrument. Some samples are analyzed total ion chromatography combustion (IC- Total).
  • Dielectric constant (D k ) and dissipation factor (D f ) were measured using a split post dipole resonator, at a frequency of 10 gigahertz (GHz). Films were equilibrated at 23-25°C, 48-52 % relative humidity (RH) environment for 24 hours before measurement in the same environment.
  • RH relative humidity
  • Peel strength values were determined according to IPC 2.4.8, “Peel Strength of Metallic Clad Laminates,” Revision C, December 1994, except that the specimen size was 12 centimeters (cm) x 12 cm with a thickness of 1 millimeter (mm). At least four resist strips having a width of 5 mm were cut from the same copper clad laminate. The test strip was peeled back 5 cm at the tab end. The clamp was attached to the peeled back end of the test strip. The specimen was fastened with the hold down fixture so that an unencumbered vertical pull could be exerted. The end of the test strip was in a vertical position ready for testing.
  • N LM/WS, where LM is the minimum load (N) and WS is the width of peel strip (mm).
  • 4,4'-BPADA was prepared by a high purity hydrolysis ring closure process as follows. 4,4'-BPADA-bisimide was hydrolyzed with aqueous NaOH at 135°C and 45 psig to form a corresponding 4,4'-BPADA-TA tetrasodium salt. The 4,4'-BPADA-TA tetrasodium salt tetrasodium salt was contacted with sulfuric acid and then washed with water to form a corresponding 4,4'- BPADA-TA. The 4,4’-BPADA-TA was then contacted with ortho-dichlorobenzene to form a reaction mixture, which was subsequently heated to form 4,4'-BPADA. The purified 4,4'-BPADA was then isolated from the reaction mixture and used for Example 1.
  • Example 1 A reaction vessel fitted with a stirrer, a heating unit, and a nitrogen inlet was charged with 1.24 g of ODA and 40 g of NMP. To this solution was added 3.222 g of the purified 4,4'-BPA- DA obtained as above and the resulting mixture was stirred over several hours at 23 °C to afford a viscous polyamic acid solution at 10 wt% solids.
  • Comparative examples 1 and 2 were prepared in an analogous manner as the method described in Example 1, using the same ratio of amine to anhydride, except that 4,4'-BPA-DA was prepared as described in U.S. Patent Nos. 4,329,291; 4,329,292; 4,329,496; and 4,340,545.
  • the resulting material was further purified by recrystallization from ortho-dichlorobenzene (Comparative Example 1) or was used directly (Comparative Example 2).
  • Table 2 shows the dynamic viscosities of the polyamic acid solutions (10 wt% solids, NMP, 25°C) of Example 1 and Comparative Examples 1-2.
  • the polyamic acid solution prepared from the purified 4,4'- BPADA obtained by a high purity hydrolysis ring closure process achieves a dynamic viscosity of 60,000 cP.
  • the polyamic acid solutions prepared from the 4,4'-BPADA that was not obtained by the high purity hydrolysis ring closure process only achieved dynamic viscosities of 16,000 cP (Comparative Example 1) and 50 cP (Comparative Example 2).
  • Table 3 shows the amounts (wt%) of impurities present in the respective 4,4'-BPADA used to prepare the polyamic acids of Example 1 and Comparative Examples 1-2.
  • the tetraacid is 4,4'-BPA-TA
  • the diacid is 4,4'-BPA-DA
  • the total acid is the sum of 4,4'-BPA-TA and 4,4'-BPA-DA
  • the imide-anhydride is 4,4'-BPA-IA (as shown in formula (4) where R is methyl)
  • the 4,4'-isomer refers to the amount of 4,4'-isomer of BPADA (rather than the corresponding 3,3'- or 3,4'-isomers of BPADA).
  • the purified 4,4'-BPADA obtained by a high purity hydrolysis ring closure process (Example 1) is >99.5 wt% of the 4,4'-isomer and has less than 0.3 wt% each of tetraacid and diacid, less than 0.3 wt% of total acid, and less than 0.03 wt% of imide-anhydride impurities, based on the total weight of the 4,4'-BPADA.
  • the comparative 4,4'-BPADA of Comparative Examples 1 and 2 did not have the same level of purity as the 4,4'-BPADA used in Example 1.
  • Example 1 The polyamic acid solution of Example 1 was solvent cast onto a clean glass substrate and heated at 100°C under a vacuum to remove the solvent to afford a film. The resulting film was removed from the substrate, transferred to a tenter frame, and heated at 150°C for 1 hour and then at 285°C for 2 hours.
  • a reaction vessel fitted with a stirrer, a heating unit, and a nitrogen inlet was charged with 6.4985 g of ODA and 100 g of NMP.
  • To this solution was added 10.1711 g of 4,4'-ODPA and the resulting mixture was stirred over several hours at 23 °C to afford a viscous polyamic acid solution at 15 wt% solids.
  • the polyamic acid solution was solvent cast onto a clean glass substrate and imidization was performed by the same method as in Example 2.
  • Table 4 shows the properties of Example 2 and Comparative Examples 3-4.
  • the film of Example 2 had lower glass transition temperature, water absorption, dielectric constant, and dissipation factor compared with the films of Comparative Examples 3 and 4.
  • the film of Example 2 had greater peel strength compared with the films of Comparative Examples 3 and 4.
  • a varnish composition comprising a polyamic acid comprising structural units derived from reaction of 5,5’-[l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3- isobenzofurandione composition with an organic diamine; and a solvent, wherein the 5,5’ -[1- methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione composition comprises: the 5,5’- [l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione; 25 ppm or less, or 0.01 to 25 ppm each of sodium ions, potassium ions, calcium ions, zinc ions, aluminum ions, titanium ions, iron ions, chromium ions, molybdenum ions, nickel ions, and phosphorus ions; 50 ppm or less, or 0.01 to 50 ppm each of
  • Aspect 2 The varnish composition of aspect 1, wherein the 5,5’-[l- methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione composition comprises: the 5,5’- [l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione; 0.0002 to 10 wt%, or 0.1 to 10 wt%, or 0.25 to 2 wt%, or 0.25 to 1 wt% of the residual 4,4'-BPA tetraacid and the residual 4,4'- BPA diacid combined; 0.01 to 50 ppm, or 0.01 to 25 ppm of sulfate ions; 0.01 to 25 ppm, or 0.01 to 10 ppm of sodium ions; and 0.01 to 25 ppm, or 0.01 to 10 ppm of chloride ions, wherein each amount is based on the total weight of the 5,5’-[
  • Aspect 3 The varnish composition of any one or more of the preceding aspects, wherein the 5,5’-[l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione composition comprises: the 5,5’-[l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione; 15 ppm or less, or 0.01 to 15 ppm, or 0.01 to 10 ppm of sulfate ions; 10 ppm or less, or 0.01 to 10 ppm, or 0.01 to 5 ppm of sodium ions; 5 ppm or less, or 0.01 to 5 ppm, or 0.01 to 2 ppm of chloride ions; 2 ppm or less, or 0.01 to 2 ppm, or 0.01 to 1 ppm of nitrate ions; and 2 ppm or less, or 0.01 to 2 ppm, or 0.01 to 1 ppm of
  • Aspect 4 The varnish composition of any one of the preceding aspects, wherein the 5,5’-[l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione composition comprises: the 5,5’-[l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione; 0.0002 to 10 wt%, or 0.1 to 10 wt%, or 0.25 to 2 wt%, or 0.25 to 1 wt% of the combination of 4,4'-BPA tetraacid and 4,4'-BPA diacid combined; 0.01 to 50 ppm, or 0.01 to 25 ppm of sulfate ions; 0.01 to 25 ppm, or 0.01 to 10 ppm of sodium ions; and 0.01 to 25 ppm, or 0.01 to 10 ppm of chloride ions, wherein each amount is based on the total weight of the 5,
  • Aspect 5 The varnish composition of any one of the preceding aspects, wherein the 5,5’-[l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione composition comprises: greater than or equal to 99 wt%, more preferably greater than or equal to 99.5 wt% of the 5,5’-[l- methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione; 0.01 to 25 ppm each of sodium ions, potassium ions, calcium ions, zinc ions, aluminum ions, titanium ions, iron ions, chromium ions, molybdenum ions, nickel ions, and phosphorus ions; 0.01 to 50 ppm each of phosphate ions, sulfate ions, chloride ions, nitrate ions, and nitrite ions; 0.0001 to 0.5 wt%, or 0.1 to 0.5
  • Aspect 6 The varnish composition of any one of the preceding aspects, wherein the organic diamine comprises one or more diamines each independently of formula
  • R is a C 6-30 aromatic or heteroaromatic hydrocarbon, a straight or branched chain C 4.20 alkylene, a C 3.8 cycloalkylene, or a halogenated derivative thereof; preferably wherein R is a divalent group of one or more of formulas: aryl, -C y H 2y - wherein y is an integer from 1 to 5 or a halogenated derivative thereof, or -(C 6 H I0 ) z - wherein z is an integer from 1 to 4; preferably wherein the organic diamine is 1,4-butane diamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9- nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3- methylheptamethylenedi amine, 4,4-dimethylh
  • Aspect 7 The varnish composition of any one of the preceding aspects, wherein the 5,5’-[l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione is made by a method comprising: hydrolyzing a 4,4'-BPADA-bisimide to form a corresponding 4,4'-BPADA tetraacid tetrasalt; contacting the 4,4'-BPADA tetraacid tetrasalt with a mineral acid to form a corresponding 4,4'-BPADA tetraacid; contacting the 4,4'-BPADA tetraacid with a halogenated solvent to form a reaction mixture, optionally wherein the halogenated solvent comprises ortho-dichlorobenzene, para- dichlorobenzene, meta-dichlorobenzene, trichlorobenzene, or a combination thereof; heating the reaction mixture to a temperature effective to form the corresponding 5,
  • Aspect 8 The varnish composition of any one of the preceding aspects, wherein the solvent is N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N- dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, N-cyclohexylpyrrolidinone, N- methylcaprolactam, l,3-dimethyl-2-imidazolidone, 1 ,2-dimethoxy ethane, 1,3-dioxane, 1,4-dioxane, tetrahydrofuran, g-butyrolactone, g-caprolactone, dimethylsulfoxide, benzophenone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diglyme, triglyme, tetraglyme, N,N- dimethylethyleneurea, N,N-dimethylprop
  • Aspect 9 An article manufactured from the varnish composition of any one of the preceding aspects, preferably wherein the article is a fiber, a layer, a coating, a cast article, a prepreg, a composite, or a laminate.
  • Aspect 10 The article of aspect 9, wherein the article is a composite comprising: a porous base material, preferably a fibrous preform comprising woven or non-woven glass fabric, a fiberglass fabric, or a carbon fiber, wherein the porous base material is coated or impregnated with the varnish composition of any one of aspects 1 to 8; preferably wherein the article is a prepreg, a sheet, a wire coating, a molded article, or a compression article.
  • a porous base material preferably a fibrous preform comprising woven or non-woven glass fabric, a fiberglass fabric, or a carbon fiber
  • the porous base material is coated or impregnated with the varnish composition of any one of aspects 1 to 8
  • the article is a prepreg, a sheet, a wire coating, a molded article, or a compression article.
  • Aspect 11 The article of aspect 9, wherein the article is a flexible metal-clad laminate comprising: a conductive metal layer, preferably wherein the conductive metal layer is copper, zinc, tin, brass, chromium, molybdenum, nickel, cobalt, aluminum, stainless steel, iron, gold, silver, platinum, titanium, an alloy thereof, or a combination thereof; the varnish composition of any one of aspects 1 to 8 at least partially disposed on the conductive metal layer; and optionally a supporting metal matrix layer, wherein the supporting metal matrix layer is disposed on a side opposite the conductive metal layer, preferably wherein the supporting metal matrix layer is a thermally conductive metal layer that is electrically isolated from the conductive metal layer, more preferably wherein the thermally conductive metal is aluminum, boron nitride, aluminum nitride, copper, iron, steel, or a combination thereof, preferably wherein the conductive metal layer is patterned to provide a printed circuit board, more preferably wherein the printed circuit board has a
  • Aspect 14 The method of aspect 14, comprising: forming a layer comprising the varnish composition of any one of aspects 1 to 10 on a substrate; removing the solvent from the layer to provide a primer layer; forming a second layer comprising a ceramic, a fluoropolymer, a thermosetting polymer, or a combination thereof on the primer layer to provide the multilayer article; and optionally thermally treating the multilayer article to cure the thermosetting polymer; wherein the second layer optionally further comprises the varnish composition of any one of aspects 1 to 10, and forming the layer further comprises removing the solvent from the second layer; wherein the ceramic is A1 2 0 3 , Ti0 2 , Zr0 2 , Cr 2 0 3 , Si0 2 , MgO, BeO; Y 2 0 3 , A1 2 0 3 -SI0 2 , MgO-Zr0 2 , SiC, WC, B C, TiC, Si 3 N 4 , TiN, BN, AIN, TiB,
  • a varnish composition comprising: a polyamic acid comprising structural units derived from reaction of 5,5’-[l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3- isobenzofurandione composition with an organic diamine; and a solvent, wherein the 5,5’ -[1- methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione composition comprises: greater than or equal to 99.5 wt% of the 5,5’-[l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3- isobenzofurandione; 0.01 to 25 ppm each of sodium ions, potassium ions, calcium ions, zinc ions, aluminum ions, titanium ions, iron ions, chromium ions, molybdenum ions, nickel ions, and phosphorus ions; 0.01 to 50 ppm each of phosphate
  • Aspect 16 The varnish composition of aspect 15, wherein the varnish composition has a dynamic viscosity that is a greater than a dynamic viscosity of a comparable varnish composition that is prepared from an 5,5’-[l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3- isobenzofurandione composition that includes less than 99.5 wt% of the 5,5’-[l- methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione, based on the total weight of the 5,5 ’ -[ 1 -methylethylidene)bis(4, 1 -phenyleneoxy)bis- 1 ,3 -isobenzofurandione composition, wherein the dynamic viscosities are determined at a solids content of 10 wt% in l-methylpyrrolidin-2-one at 25°C.
  • Aspect 17 The varnish composition of any one of the preceding aspects, wherein a film derived from the varnish composition has a T g that is a less than a T g of a comparable varnish composition that is prepared from an 5,5’-[l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3- isobenzofurandione composition that includes less than 99.5 wt% of the 5,5’-[l- methylethylidene)bis(4,l-phenyleneoxy)bis- 1,3 -isobenzofurandione, based on the total weight of the 5,5 ’ -[ 1 -methylethylidene)bis(4, 1 -phenyleneoxy)bis- 1 ,3 -isobenzofurandione composition, wherein the dynamic viscosities are determined at a solids content of 10 wt% in l-methylpyrrolidin-2-one at 25°C.
  • Aspect 18 The varnish composition of any one of the preceding aspects, wherein the 5,5’-[l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione composition comprises: the 5,5’-[l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione; 0.0001 to 1 wt% of residual 4,4'-BPA tetraacid; 0.0001 to 1 wt% of residual 4,4'-BPA diacid; and 0.00001 to 0.1 wt% of residual 4,4'-BPA imide-anhydride, wherein each amount is based on the total weight of the 5,5’-[l- methylethylidene)bis(4,l-phenyleneoxy)bis- 1,3 -isobenzofurandione composition, and wherein the 5,5’-[l-methylethylidene)bis(4,l-phenylene
  • Aspect 18 The varnish composition of any one of the preceding aspects, wherein the 5,5’-[l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione composition comprises: the 5,5’-[l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione; and 0.00001 to 0.1 wt% of residual 4,4'-BPA imide-anhydride, based on the total weight of the 5,5’-[l- methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione composition, wherein the 5,5’- [l-methylethybdene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione composition comprises greater than or equal to 99.5 wt% of the 5,5’-[l-methylethylidene)bis(
  • a varnish composition comprising apolyamic acid comprising structural units derived from reaction of 5,5’-[l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3- isobenzofurandione composition with an organic diamine; and a solvent, wherein the 5,5’ -[1- methylethybdene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione composition comprises: the 5,5’- [l-methylethybdene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione; 25 ppm or less, or 0.01 to 25 ppm each of sodium ions, potassium ions, calcium ions, zinc ions, aluminum ions, titanium ions, iron ions, chromium ions, molybdenum ions, nickel ions, and phosphorus ions; 50 ppm or less, or 0.01 to 50 ppm each of
  • a varnish composition comprising apolyamic acid comprising structural units derived from reaction of 5,5’-[l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3- isobenzofurandione composition with an organic diamine; and a solvent, wherein the 5,5’ -[1- methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione composition comprises: the 5,5’- [l-methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione; 0.00001 to 0.1 wt% of residual 4,4'-BPA imide-anhydride, based on the total weight of the 5,5’-[l- methylethylidene)bis(4,l-phenyleneoxy)bis-l,3-isobenzofurandione composition, wherein a dynamic viscosity of the varnish composition
  • compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed.
  • the compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.
  • test standards are the most recent standard in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.
  • hydrocarbon refers to any compound, group, or substituent that includes carbon and hydrogen.
  • Aliphatic means a non-aromatic hydrocarbon group.
  • Alkyl means a branched or straight chain, unsaturated aliphatic hydrocarbon group.
  • Cycloalkyl means a mono- or polycyclic alkyl group, wherein all ring members are carbon.
  • Alkenyl means a straight or branched chain, monovalent hydrocarbon group having at least one carbon-carbon double bond.
  • Alkoxy means an alkyl group that is linked via an oxygen (i.e., alkyl-O-).
  • Alkylene means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group.
  • Cycloalkylene means a divalent cycloalkyl group, wherein all ring members are carbon.
  • Cycloalkenyl means a mono- or polycyclic alkenyl group, wherein all ring members are carbon.
  • Aryl means a mono- or polycyclic aromatic hydrocarbon group, wherein all ring members are carbon.
  • Arylene means a divalent aryl group.
  • Alkylaryl means an aryl group substituted with an alkyl group.
  • Arylalkyl means an alkyl group substituted with an aryl group.
  • halo means a group or compound including one more halogen substituents that can be the same or different.
  • hetero means that the compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) are each independently N, O, S, Si, or P.
  • each of the foregoing groups can be unsubstituted or substituted, provided that the substitution does not significantly adversely affect synthesis, stability, or use of the compound.
  • “Substituted” means that the compound, group, or atom is substituted with at least one (e.g., 1, 2, 3, or 4) substituents that can each independently be a nitro (-NO 2 ), cyano (-CN), hydroxy (-OH), halogen, thiol (-SH), thiocyano (-SCN), Ci-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, Ci-6 haloalkyl, C 1-9 alkoxy, Ci-6 haloalkoxy, C 3-12 cycloalkyl, C 5-18 cycloalkenyl, C 6-12 aryl, C 7-13 arylalkyl (e.g., benzyl), C 7-12 alkylaryl (e.g., tolu).

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Abstract

L'invention concerne une composition de vernis, comprenant un acide polyamique comprenant des motifs structuraux dérivés de la réaction d'une composition de 5,5'-[1-méthyléthylidène)bis(4,1-phénylèneoxy)bis-1,3-isobenzofurandione avec une diamine organique ; et un solvant, la 5,5'-[1-méthyléthylidène)bis(4,1-phénylèneoxy)bis-1,3-isobenzofurandione comprenant la 5,5'-[1-méthyléthylidène)bis(4,1-phénylèneoxy)bis-1,3-isobenzofurandione ; 25 ppm ou moins de chacun des ions sodium, potassium, calcium, zinc, aluminium, titane, fer, chrome, molybdène, nickel et phosphore ; 50 ppm ou moins de chacun des ions phosphate, sulfate, chlorure, nitrate et nitrite ; 0,0001 à 10 % en poids de tétraacide de 4,4'-BPA résiduel ; 0,0001 à 10 % en poids de diacide de 4,4'-BPA résiduel ; et 0,00001 à 4 % en poids d'anhydride de 4,4'-BPA-imide résiduel, la viscosité dynamique de la composition de vernis étant de 30 000 à 10 000 cP à 25 °C, et un produit durci de la composition de vernis ayant une Tg de 150 à 300 °C, de préférence la composition de 5,5'-[1-méthyléthylidène)bis(4,1-phénylèneoxy)bis-1,3-isobenzofurandione comprenant plus de 99 % en poids de la 5,5'-[1-méthyléthylidène)bis(4,1-phénylèneoxy)bis-1,3-isobenzofurandione.
PCT/US2020/063078 2019-12-03 2020-12-03 Vernis d'acide polyamique préparé à partir de dianhydride de bisphénol a de haute pureté et articles préparés à partir de celui-ci WO2021113489A1 (fr)

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Cited By (1)

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CN115558383A (zh) * 2022-10-20 2023-01-03 辽宁合为科技有限公司 一种导热涂层材料及地暖模块

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